US4761440A - Articles of filled synthetic polymeric materials and glass bead filler therefor - Google Patents

Articles of filled synthetic polymeric materials and glass bead filler therefor Download PDF

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US4761440A
US4761440A US07/041,667 US4166787A US4761440A US 4761440 A US4761440 A US 4761440A US 4166787 A US4166787 A US 4166787A US 4761440 A US4761440 A US 4761440A
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beads
glass beads
synthetic polymer
article
filler material
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Pierre Laroche
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AGC Glass Europe SA
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Glaverbel Belgium SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2996—Glass particles or spheres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention relates to synthetic polymeric articles incorporating glass beads as filler material, and to glass bead filler materials for use in the preparation of such articles.
  • glass beads used as a synthetic polymer filler
  • various mechanical strength properties of articles formed from the synthetic polymeric material such as their flexibility and tensile strength
  • the presence of the beads often has an adverse effect on the impact strength of the articles. This is particularly the case when using solid, as distinct from hollow, glass beads.
  • the present invention enables this adverse effect on impact strength to be avoided or reduced.
  • the invention is based on the discovery that a degree of shock-resistance can be given to articles moulded from the filled synthetic polymer by suitably surface coating the glass beads used as filler.
  • a synthetic polymeric article incorporating glass beads as filler material characterised in that the glass bead filler material comprises beads bearing coatings of at least one coating agent in a total coating amount not exceeding 1% by weight of the uncoated beads, which coatings limit adhesion between the glass and the synthetic polymeric material and confer an increased impact resistance on the article as compared with an article which includes uncoated glass beads as filler but is otherwise identical.
  • the invention also includes mouldable or otherwise formable synthetic polymeric material incorporating glass beads as a filler, characterised in that the beads bear coatings of at least one coating agent in a total coating amount not exceeding 1% by weight of the uncoated beads, which coatings limit adhesion between the glass and the synthetic polymeric material and confer an increased impact resistance on articles when formed from such filled synthetic polymeric material as compared with an article which includes uncoated glass beads as filler but is otherwise identical.
  • the sole FIGURE is a graph comparing the impact resistance of sheets of epoxy-amine resin filled with solid glass beads as a function of bead concentration for styrene-butadiene coated beads (curve 1) and uncoated beads (curve 2).
  • said coating amount is between 0.02% and 0.2% by weight of the uncoated beads.
  • said coating amount is not more than 0.1% by weight of the uncoated beads. Good results have been obtained, for example, when using polymeric coating material in an amount of about 0.2 to 1.0 g per kg of glass beads having a specific surface of 0.3 m 2 /cm 3 .
  • Adhesion between the glass and the synthetic polymeric material may for example, be limited by using a coating agent which bonds well to glass but has a limited adherence to synthetic polymeric material, or by using a coating agent which bonds well to synthetic polymeric materials, but less well to glass.
  • coating agents having a limited adherence to synthetic polymeric materials may be used in the performance of this invention.
  • coating agents are silicones, silanes--especially silicon-functional silanes, and oleophobic fluorocarbon compounds. It is preferred that said coatings comprise a silane and/or a fluorocarbon compound.
  • Such materials can be arranged to bond well to glass, while having a limited capacity to adhere to synthetic polymeric materials. This has the advantage of forming a coating which confers the required properties while at the same time being resistant to removal from the beads during handling prior to incorporation in a synthetic polymeric material.
  • said coatings comprise a synthetic polymeric material having shock-absorbing properties.
  • a synthetic polymeric material having shock-absorbing properties adhere less well to glass beads, and so are more apt to be removed by careless handling prior to incorporation in synthetic polymer material as filler, but it has been found that when so incorporated beads coated in this way tend to confer a greater improvement in impact strength on synthetic polymeric articles.
  • Suitable synthetic polymeric materials for coating beads for use in the manufacture of products according to this invention include elastomers properly so called and other polymers incorporating chain units or segments which undergo straightening or change in orientation under stress, with consequent energy-absorption.
  • coating material must normally be capable of energy absorption at ordinary room temperature which implies a low glass transition (T g ) temperature.
  • T g glass transition temperature
  • Such an energy-absorbing synthetic polymeric material is preferably a material for which the glass transition temperature (T g ), determined by differential scanning calorimetry, is lower than 15° C.
  • the beads Prior to coating the beads with a synthetic polymeric material, they can be treated with a coupling agent to promote required adhesion of the polymer coating to the beads, and it is preferred that the adhesion of said polymeric coatings to the glass beads is influenced by the presence of a coupling agent comprising a silane.
  • a coupling agent comprising a silane.
  • the coupling agents used for this purpose are customarily selected to achieve as strong an interfacial bond as possible because a strong adhesion benefits various strength properties, for example, the flexural strength and modulus of the composite material.
  • any coupling agent used should not be selected with the object of making the interfacial bond as strong as possible because a very high strength is not helpful to the main purpose for which the beads are coated. A very strong adhesion can prevent full exploitation of the ability of the coatings to improve the impact strength of a formed article.
  • the coupling agent can be selected to anchor the polymer via its rigid or less deformable structural segments or units, leaving the other parts of the molecular structure free to undergo reorientation under stress.
  • the strength of the interfacial bond actually achieved can be controlled by mixing one coupling compound with another to form a composite coupling agent, and it is especially preferred that said coupling agent comprises a mixture of different silanes and forms an interfacial bond of a strength intermediate that attainable by either component if used alone.
  • a particularly suitable energy-absorbing coating is one formed of a styrene-butadiene copolymer such as that commercially available from Polysar Europe S.A. of Zwijndrecht, Belgium and designated X818.
  • a styrene-butadiene copolymer the styrene units have a T g of 60°-70° C., but the T g of the butadiene units, which are responsible for the required energy-absorbing property of the material, is below 15° C.
  • Another useful bead coating material is copoly(NH 2 -butadiene-acrylonitrile-NH 2 ).
  • copoly(butylacrylate-epoxyacrylate) can be used. However there are reservations in recommending the latter material because acrylic polymers have poor resistance to temperatures which are normally (depending on the composition of the synthetic polymeric matrix material) employed in moulding operations.
  • the bead coatings can be formed by application of the coating material as a solution or as a latex (aqueous suspension). It suffices for the beads to be immersed in the coating material, drained and dried.
  • Glass beads of any of a wide range of specifications can be selected for use in carrying out the present invention.
  • the size and form of the beads are of influence, as known per se in relation to fillers, on the properties of articles formed from the composite material.
  • the beads are solid.
  • Solid beads are particularly preferred as filler for thermoplastic resins because of their greater crush resistance.
  • the invention enables the particular benefits of solid glass beads as a filler, including their inherent strength which is an advantage for the forming operation as well as for the properties of the moulded product, to be combined with that of a higher product impact strength than that which would normally be attainable with such beads. Normally, the lowering of impact strength resulting from the use of glass beads as synthetic polymer filler is particularly marked if the beads are solid.
  • the glass beads used in carrying out the invention are preferably spherical in order to realise the benefits for the flow properties of the filled synthetic polymer, and in order to promote even stress distribution within articles formed therefrom, which is known to be associated with a filler of that form.
  • the size of the beads is a factor which influences the properties of a material according to the present invention in the same way as in known materials using uncoated glass beads as the filler. It is generally appropriate to use beads less than 500 ⁇ m in diameter and for most purposes it is recommended to use beads of a much smaller maximum diameter, for example, beads of diameters less than 200 ⁇ m.
  • the beads preferably have a narrow size range distribution (and therefore a low apparent bulk density) because they can then be better distributed in the formable matrix material so that shock is transmitted through the resin and not directly from bead to bead.
  • their apparent bulk density is from 1.5 to 1.55. If the beads are confined to a narrow size range, the viscosity of the formable material incorporating the beads increases steeply with increase in the bead/matrix quantity ratio and this must be taken into account when selecting this ratio for a particular composite material.
  • the glass beads have a granulometry such that 90% of the beads have a diameter smaller than a length x and 10% of the beads have a diameter smaller than a length y, the values of x and y being such that x-y is greater than 45 ⁇ m but smaller than 65 ⁇ m.
  • the beads are preferably made of a soda-lime glass (A glass).
  • An article or formable material according to the invention can incorporate filler comprising the coated glass beads and at least one other kind of discrete material.
  • the filler may comprise in addition to the coated glass beads, a finely divided material which modifies the bulk density of the filler.
  • a finely divided material can for example serve to reduce the extent to which the viscosity of the synthetic polymer/bead mixture increases with increase in the bead/synthetic polymer quantity ratio.
  • Such finely divided material can, with advantage, be a hydrophobic, inorganic substance which is substantially chemically inert with respect to the beads and has a specific surface of at least 50 m 2 /g.
  • compositions incorporating such a composite filler and wherein the said hydrophobic finely divided component is present in an amount not more than 5% by weight of the glass beads are described and claimed in our co-pending United Kingdom Patent Application No. 83 31 375, filed Nov. 24. 1983.
  • Particularly recommended materials for the finely divided hydrophobic component of the filler are the silicas commercially available from Degussa (Frankfurt) under their Trade Mark AEROSIL and from Cabot Corporation (Tuscola, Ill.) under their Trade Mark CAB-O-SIL.
  • the selection of the bead coating material for a particular kind of composite should take account of the composition of the mouldable matrix material into which the coated glass beads are to be incorporated.
  • the strength of the interfacial bond between the bead coatings and the matrix is a factor which can influence the tensile and bending strengths of the product as well as its impact resistance.
  • a low adhesion which is desirable for promoting impact strength can adversely affect bending strength and modulus, and if all of these factors are important for a given product, the selected combination of matrix material and adhesion limiting bead coating material should represent an appropriate compromise.
  • the strength of the adhesion is dependent on the surface tension difference between the bead coatings and the matrix.
  • the synthetic polymeric matrix material can be a thermoplastic, for example, a polyamide or polystyrene, or a thermosetting resin, for example, an epoxy or polyester resin.
  • a thermoplastic for example, a polyamide or polystyrene
  • a thermosetting resin for example, an epoxy or polyester resin.
  • the mixing of the coated beads with the matrix material is easier if this material is in liquid state as is the case, for example, when using a two-component epoxy resin composition.
  • the quantity ratio of coated beads to synthetic polymeric matrix material is a factor of importance in various respects.
  • the benefits for impact resistance increase, within a certain range, with the proportion of coated beads in the composite material. Above a certain concentration of the beads, the impact resistance begins to decrease because of direct bead to bead contacts.
  • the proportion of coated beads is preferably from 30 to 40% by weight.
  • Composites according to the invention can be used in the manufacture of a wide variety of articles, for example, articles of houseware, machine and structural components and decorative and/or functional fittings.
  • articles in the latter category is an instrument panel such as for a vehicle.
  • the invention includes coated glass beads suitable for use as a synthetic polymer filler, said beads being characterised in that the beads bear surface coatings of synthetic polymeric material of which the glass transition temperature (T g ), determined by differential scanning calorimetry, is lower than 15° C.
  • T g glass transition temperature
  • coated beads may and preferably do have any of the optional features hereinbefore referred to in relation to coated beads incorporated as filler into a composite according to the invention.
  • a filler according to the present invention, for use in a synthetic polymeric matrix material was prepared by coating a batch of solid spherical glass beads with a polymeric coating material.
  • the mean diameter of the glass beads (i.e. the diameter which is such that half of the beads were above and half of them were below such mean) was 26 ⁇ m. 90% of the beads had a diameter below 58 ⁇ m and 10% had a diameter below 11 ⁇ m.
  • the beads were immersed in a latex, i.e., in an aqueous solution comprising a styrene-butadiene copolymer (T g of the butadiene units: below 15° C.) and a coupling agent comprising phenylsilane and aminosilane.
  • a latex i.e., in an aqueous solution comprising a styrene-butadiene copolymer (T g of the butadiene units: below 15° C.) and a coupling agent comprising phenylsilane and aminosilane.
  • the beads wetted with such a latex were subsequently dried.
  • the amount of copolymer forming the bead coatings was 1 g per kg of beads of which the specific surface was 0.3 m 2 /cm 3 .
  • Such coatings have a negligible or very low adherence to epoxy resin and low adherence to the glass beads.
  • coated beads according to the invention were then mixed in a weight ratio of 1:1 with a matrix composition comprising an epoxy resin designated 818 marketed by Shell International together with a polyamine hardener marketed under the Trade Mark VERSAMID 140 by General Mills Co. and the resulting mixture was formed by extrusion into an article according to the present invention, the article being in the form of a sheet 3 mm in thickness.
  • a matrix composition comprising an epoxy resin designated 818 marketed by Shell International together with a polyamine hardener marketed under the Trade Mark VERSAMID 140 by General Mills Co.
  • a disc of this sheet material having a diameter of 3 cm was subjected to ASTM Impact Resistance Test D 2794.
  • the impact resistance of the composite was found to be 2.00 kg.cm/mm.
  • a composite having the same composition except that the beads were not coated with the styrene-butadiene copolymer was formed into a sheet of the same thickness as the one above referred to and a sample of this further sheet material having the same dimensions as the above tested sample, was subjected to the same ASTD test.
  • This sample was found to have an impact resistance of only 1.35 kg.cm/mm.
  • a disc of the same size was formed from the copolymer alone, without filler, was also subjected to the same test. It had an impact resistance of about 2 kg.cm/mm.
  • a synthetic polymer filler according to the invention was prepared by coating a batch of solid spherical glass beads having a mean diameter of 46.5 ⁇ m, 90% of the beads being below 73 ⁇ m and 10% of them being below 28 ⁇ m in diameter.
  • the beads were treated with coupling agent and coated with styrene-butadiene copolymer in the same way as the glass beads in Example 1.
  • the beads were used as filler in preparing a mouldable composite.
  • the composite was prepared in the same way as in Example 1, using the same matrix material as in that Example, but the coated beads were used in a proportion of 33% by weight of the matrix material.
  • the impact resistance of the composite was found to be 1.77 kg.cm/mm.
  • the impact resistance of a composite of the same composition except that the beads were uncoated was found to be 1.25 kg.cm/mm.
  • a filler according to the invention was prepared as in Example 1, but using a batch of solid spherical glass beads having a mean diameter of 66 ⁇ m, 90% of the beads being below 103 ⁇ m and 10% of them being below 42 ⁇ m in diameter.
  • the beads were treated with coupling agent and coated with styrene-butadiene copolymer in the same way as the beads in Example 1.
  • the beads were used as a filler in preparing a mouldable composite.
  • the composite was prepared in the same way as in Example 1, using the same matrix material and the same coated bead/matrix ratio. The impact resistance of the composite was again found to be improved by the presence of the bead coatings.
  • Coated beads identical with those used as the filler in Example 1 were used as the filler in a composite comprising Nylon 6/6 marketed under the Trade Mark MARANYL by Imperial Chemical Industries Limited.
  • the bead coatings have an adherence to polyamides which is very low.
  • the beads were used in a proportion of 15% by weight of the matrix material.
  • the coated beads were mixed with the nylon powder within the screw of an extruder from which the composite was extruded as a rod. The rod was then cut into pieces which were supplied to an injection moulding apparatus for forming into moulded articles.
  • coated beads and nylon within an extruder can be mixed in some other mixing appliance and the mixture can then be directly injection moulded. However, this is not so suitable a procedure for industrial scale operations.
  • Example 4 An impact resistance better than that realised by the bead coatings in Example 4 was obtained when using an aliphatic polyurethane latex containing at least 10% of plasticiser for forming the bead coatings limiting adherence to the nylon instead of the styrene-butadiene polymer latex.
  • This latter material is a fluoro-alkyl-sulphonate of potassium.
  • the coating was formed by mixing the beads with a solution of the coating agent and then drying the beads to leave coating deposits of the amounts indicated in grams of the coating agent per kilogram of the beads. The results are shown in Table I.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Farming Of Fish And Shellfish (AREA)
US07/041,667 1984-07-12 1987-04-20 Articles of filled synthetic polymeric materials and glass bead filler therefor Expired - Lifetime US4761440A (en)

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GB8417740 1984-07-12
GB848417740A GB8417740D0 (en) 1984-07-12 1984-07-12 Articles of filled plastics materials

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US07/175,286 Division US4882367A (en) 1984-07-12 1988-03-30 Articles of filled synthetic polymeric materials and glass bead filler therefore

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US5348763A (en) * 1987-05-14 1994-09-20 Glaverbel Method of forming a polymeric matrix containing filler material
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US5733497A (en) * 1995-03-31 1998-03-31 Dtm Corporation Selective laser sintering with composite plastic material
WO1999054395A1 (fr) * 1998-04-22 1999-10-28 Walters, Craig, Andrew Matiere resistant a l'usure
US6060155A (en) * 1998-02-06 2000-05-09 The Budd Company Polymeric forming tool
US6074506A (en) * 1992-04-16 2000-06-13 The Budd Company Method of bonding using non-compressible beads
US6180199B1 (en) 1992-04-16 2001-01-30 The Budd Company Beaded adhesive and hem flanged part made therefrom
US6696147B1 (en) 1992-04-16 2004-02-24 Thyssenkrupp Budd Company Beaded adhesive and flanged part made therefrom
US20200398484A1 (en) * 2018-03-09 2020-12-24 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN114685982A (zh) * 2022-03-25 2022-07-01 上海金发科技发展有限公司 一种改性聚酰胺组合物及制备方法和应用
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US6519774B2 (en) 2001-06-11 2003-02-18 Joan L. Mitchell Scuba wet suit with constant buoyancy
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5049594A (en) * 1985-08-30 1991-09-17 Ecc International Limited Polymer compositions containing inorganic fillers coated with latex and process for preparing coated fillers
US5348763A (en) * 1987-05-14 1994-09-20 Glaverbel Method of forming a polymeric matrix containing filler material
US5128203A (en) * 1988-02-19 1992-07-07 Glaverbel Marking comprising glass beads in a matrix
US5458973A (en) * 1989-07-24 1995-10-17 Ecc International Ltd. Granular filler
US6696147B1 (en) 1992-04-16 2004-02-24 Thyssenkrupp Budd Company Beaded adhesive and flanged part made therefrom
US6074506A (en) * 1992-04-16 2000-06-13 The Budd Company Method of bonding using non-compressible beads
US6180199B1 (en) 1992-04-16 2001-01-30 The Budd Company Beaded adhesive and hem flanged part made therefrom
US20040163771A1 (en) * 1992-04-16 2004-08-26 Herring James M. Apparatus for dispensing beaded adhesives
US5733497A (en) * 1995-03-31 1998-03-31 Dtm Corporation Selective laser sintering with composite plastic material
US6060155A (en) * 1998-02-06 2000-05-09 The Budd Company Polymeric forming tool
WO1999054395A1 (fr) * 1998-04-22 1999-10-28 Walters, Craig, Andrew Matiere resistant a l'usure
US11898060B2 (en) * 2014-03-05 2024-02-13 Hempel A/S Anti-corrosive zinc primer coating compositions
US20200398484A1 (en) * 2018-03-09 2020-12-24 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN114685982A (zh) * 2022-03-25 2022-07-01 上海金发科技发展有限公司 一种改性聚酰胺组合物及制备方法和应用
CN114685982B (zh) * 2022-03-25 2024-03-12 上海金发科技发展有限公司 一种改性聚酰胺组合物及制备方法和应用

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NL192794B (nl) 1997-10-01
GB2161489B (en) 1987-11-25
GB8417740D0 (en) 1984-08-15
DE3524665C2 (de) 2000-11-30
IT1183911B (it) 1987-10-22
JPS6136340A (ja) 1986-02-21
ES8704860A1 (es) 1987-05-01
NL8501961A (nl) 1986-02-03
DE3524665A1 (de) 1986-01-16
IT8567600A0 (it) 1985-07-01
FR2567530A1 (fr) 1986-01-17
GB2161489A (en) 1986-01-15
JPH066670B2 (ja) 1994-01-26
FR2567530B1 (fr) 1988-02-19
BE902793A (fr) 1986-01-02
ZA855223B (en) 1986-03-26
ES545371A0 (es) 1987-05-01
LU85985A1 (fr) 1986-02-12
AT390798B (de) 1990-06-25
US4879321A (en) 1989-11-07
US4882367A (en) 1989-11-21
GB8514233D0 (en) 1985-07-10
ATA205985A (de) 1989-12-15
NL192794C (nl) 1998-02-03

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